phenyl N-ethylthionocarbamate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: phenyl N-ethylthionocarbamate
• 英文别名: phenyl N-ethylthio-carbamate；O-phenyl N-ethylcarbamothioate
• 化学式: C₉H₁₁NOS
• 分子量: 181.258
• InChiKey: NMNGRBIGWHKPFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  53.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  phenyl ethylcarbamate 在 劳森试剂 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 phenyl N-ethylthionocarbamate
  参考文献：
  名称：

  芳基N-乙基硫代氨基甲酸酯的氨解：O和S对对反应性和机理的协同作用

  摘要：

  在30.0°C下研究了芳基N-乙基硫代氨基甲酸酯（ETNC / EtHN-C（S）-OC 6 H 4 Z）与苄胺（XC 6 H 4 CH 2 NH 2）的氨解反应。ETNC的速度减慢了大约两倍。与芳基N-乙基硫代氨基甲酸酯的相应氨解反应（AETC / EtHN-（C O）-SC 6 H 4 Z）相比，它的原子分解反应要比图3所示，这是根据原子对O和S对反应性和机理的协同作用来解释的。对于一致的过程，这些效应可预测速率序列-C（S）-S- <-C（S）-O- <-C-（O）-S- <-C-（O）-O-，并且当前结果与此顺序一致。负交叉相互作用常数，ρ XZ = -0.87，的幅度β Ž（= 0.36-0.50）和失败的RSP的是在与该协同机制一致。涉及氘化苄胺的正常动力学同位素效应k H / k D = 1.52-1.78表明存在氢键合的环状过渡态。还讨论了影响该机制的其他因素。

  DOI：

  10.1021/jo050606b

文献信息

• Aminolyses of 4-Nitrophenyl Phenyl Carbonate and Thionocarbonate:  Effect of Modification of Electrophilic Center from CO to CS on Reactivity and Mechanism
  作者：Ik-Hwan Um、Eun Young Kim、Hye-Ran Park、Sang-Eun Jeon

  DOI：10.1021/jo052417z

  日期：2006.3.1

  [GRAPHICS]A kinetic study is reported for nucleophilic substitution reactions of 4-nitrophenyl phenyl carbonate (5) and 4-nitrophenyl phenyl thionocarbonate (6) with a series of primary amines. The thiono compound 6 is less reactive than its oxygen analogue 5 toward strongly basic amines but is more reactive toward weakly basic CF3CH2NH2. The Bronsted-type plots obtained from the aminolyses of 5 and 6 are curved downwardly. The reactions are proposed to proceed through a stepwise mechanism with a change in the RDS on the basis of the curved Bronsted-type plots. The microscopic rate constants (k(1) and k(2)/k(-1) ratio) associated with the current aminolyses are consistent with the proposed reaction mechanism. The replacement of the C=O bond in 5 by a polarizable C=S group results in a decrease in the k(1) value but an increase in the k(2)/k(-1) ratio. Besides, such a modification of the electrophilic center causes a decrease in pK(a)degrees, defined as the pK(a) at the curvature center of curved Bronsted-type plots, but does not alter the reaction mechanism. The larger k(2)/k(-1) ratio for the reactions of 6 compared to those of 5 is proposed to be responsible for the decreased pK(a)degrees value.
• Aminolysis of Aryl <i>N</i>-Ethyl Thionocarbamates: Cooperative Effects of Atom Pairs O and S on the Reactivity and Mechanism
  作者：Hyuck Keun Oh、Ji Young Oh、Dae Dong Sung、Ikchoon Lee

  DOI：10.1021/jo050606b

  日期：2005.7.1

  with benzylamines (XC6H4CH2NH2) in acetonitrile are investigated at 30.0 °C. The rate of ETNC is slower by a factor of ca. 3 than the corresponding aminolysis of aryl N-ethyl thiocarbamate (AETC/EtHN-(CO)-SC6H4Z), which has been interpreted in terms of cooperative effects of atom pairs O and S on the reactivity and mechanism. For concerted processes, these effects predict a rate sequence, −C(S)−S− <

  在30.0°C下研究了芳基N-乙基硫代氨基甲酸酯（ETNC / EtHN-C（S）-OC 6 H 4 Z）与苄胺（XC 6 H 4 CH 2 NH 2）的氨解反应。ETNC的速度减慢了大约两倍。与芳基N-乙基硫代氨基甲酸酯的相应氨解反应（AETC / EtHN-（C O）-SC 6 H 4 Z）相比，它的原子分解反应要比图3所示，这是根据原子对O和S对反应性和机理的协同作用来解释的。对于一致的过程，这些效应可预测速率序列-C（S）-S- <-C（S）-O- <-C-（O）-S- <-C-（O）-O-，并且当前结果与此顺序一致。负交叉相互作用常数，ρ XZ = -0.87，的幅度β Ž（= 0.36-0.50）和失败的RSP的是在与该协同机制一致。涉及氘化苄胺的正常动力学同位素效应k H / k D = 1.52-1.78表明存在氢键合的环状过渡态。还讨论了影响该机制的其他因素。